Encapsulated fragrance chemicals

ABSTRACT

A polymeric encapsulated fragrance is disclosed which is suitable for use in personal care and cleaning products. In a preferred embodiment of the invention, the fragrance is encapsulated by a first polymer material to form a fragrance encapsulated polymer, the polymer encapsulated shell is then coated with a mixture of cationic polymers, in a preferred embodiment the coating polymers are a reaction product of polyamines (including 1H-imidazole) and (chloromethyl) oxirane or (bromomethyl) oxirane.

This is a Continuation-in-Part (CIP) of prior application Ser. No.10/460,434 filed on Jun. 12, 2003 which, in turn, is acontinuation-in-part of application for U.S. Letters Patent, Ser. No.10/268,526 filed Oct. 10, 2002.

FIELD OF THE INVENTION

The present invention relates to fragrance materials that areencapsulated with a polymeric material, the encapsulated fragrancematerials are further coated with a cationic polymer material. Theencapsulated fragrance materials are well suited for rinse-offapplications associated with personal care and cleaning products.

BACKGROUND OF THE INVENTION

Fragrance chemicals are used in numerous products to enhance theconsumer's enjoyment of a product. Fragrance chemicals are added toconsumer products such as laundry detergents, fabric softeners, soaps,detergents, personal care products, such as shampoos, body washes,deodorants and the like, as well as numerous other products.

In order to enhance the effectiveness of the fragrance materials for theuser, various technologies have been employed to enhance the delivery ofthe fragrance materials at the desired time. One widely used technologyis encapsulation of the fragrance material in a protective coating.Frequently the protective coating is a polymeric material. The polymericmaterial is used to protect the fragrance material from evaporation,reaction, oxidation or otherwise dissipating prior to use. A briefoverview of polymeric encapsulated fragrance materials is disclosed inthe following U.S. patents: U.S. Pat. No. 4,081,384 discloses a softeneror anti-stat core coated by a polycondensate suitable for use in afabric conditioner; U.S. Pat. No. 5,112,688 discloses selected fragrancematerials having the proper volatility to be coated by coacervation withmicro particles in a wall that can be activated for use in fabricconditioning; U.S. Pat. No. 5,145,842 discloses a solid core of a fattyalcohol, ester, or other solid plus a fragrance coated by an aminoplastshell; and U.S. Pat. No. 6,248,703 discloses various agents includingfragrance in an aminoplast shell that is included in an extruded barsoap.

While encapsulation of fragrance in a polymeric shell can help preventfragrance degradation and loss, it is often not sufficient tosignificantly improve fragrance performance in consumer products.Therefore, methods of aiding the deposition of encapsulated fragranceshave been disclosed. U.S. Pat. No. 4,234,627 discloses a liquidfragrance coated with an aminoplast shell further coated by a waterinsoluble meltable cationic coating in order to improve the depositionof capsules from fabric conditioners. U.S. Pat. No. 6,194,375 disclosesthe use of hydrolyzed polyvinyl alcohol to aid deposition offragrance-polymer particles from wash products. U.S. Pat. No. 6,329,057discloses use of materials having free hydroxy groups or pendantcationic groups to aid in the deposition of fragranced solid particlesfrom consumer products.

Despite these and many other disclosures there is an ongoing need forthe improved delivery of fragrance materials for various rinse-offproducts that provide improved performance.

SUMMARY OF THE INVENTION

The present invention is directed to a polymer encapsulated fragrance,the polymer encapsulated fragrance being further treated with a cationicpolymer to improve deposition.

More specifically the present invention is directed to a compositioncomprising:

A fragrance material; said fragrance material encapsulated by a polymerto create a polymer encapsulated fragrance; the polymer encapsulatedfragrance being further coated by a cationic polymer. In a preferredembodiment of the invention the cationic polymer is selected from thegroup consisting of cationic polyamide and a cationic heterocyliccompound and mixtures thereof. In a highly preferred embodiment of theinvention the cationic material comprises 1H-imidaaole polymer with(chloromethyl oxirane) and 1,6 hexanediamine, N-(6-aminohexyl)-polymerwith (chloromethyl) oxirane. In particular, reaction products of1H-imidazole and (chloromethyl) oxirane, known under Chemical AbstractService number (CAS) 68797-57-9. Also preferred is a polymer comprising1,6-hexanediamine,N-(6-aminohexyl) with (chloromethyl) oxirane, knownunder CAS number 67953-56-4. These materials are available RegencyChemicals, Leics, England. A method for making the cationic coatedpolymer encapsulated fragrances is also disclosed.

The present invention is well suited for use in rinse off products,which are products that are applied to a substrate and then removed insome manner. Especially preferred products that use the cationic coatedpolymer encapsulated fragrance of the present invention include, withoutlimitation, hair and pet shampoos, hair conditioners, laundrydetergents, fabric conditioners and the like. These and otherembodiments of the present invention will become apparent upon referringto the following figure and description of the invention.

DETAILED DESCRIPTION OF THE INVENTION

The fragrances suitable for use in this invention include withoutlimitation, any combination of fragrance, essential oil, plant extractor mixture thereof that is compatible with, and capable of beingencapsulated by a polymer.

Many types of fragrances can be employed in the present invention, theonly limitation being the compatibility and ability to be encapsulatedby the polymer being employed, and compatability with the encapsulationprocess used. Suitable fragrances include but are not limited to fruitssuch as almond, apple, cherry, grape, pear, pineapple, orange,strawberry, raspberry; musk, flower scents such as lavender-like,rose-like, iris-like, and carnation-like. Other pleasant scents includeherbal scents such as rosemary, thyme, and sage; and woodland scentsderived from pine, spruce and other forest smells. Fragrances may alsobe derived from various oils, such as essential oils, or from plantmaterials such as peppermint, spearmint and the like. Other familiar andpopular smells can also be employed such as baby powder, popcorn, pizza,cotton candy and the like in the present invention.

A list of suitable fragrances is provided in U.S. Pat. Nos. 4,534,891,5,112,688 and 5,145,842. Another source of suitable fragrances is foundin Perfumes Cosmetics and Soaps, Second Edition, edited by W. A.Poucher, 1959. Among the fragrances provided in this treatise areacacia, cassie, chypre, cylamen, fern, gardenia, hawthorn, heliotrope,honeysuckle, hyacinth, jasmine, lilac, lily, magnolia, mimosa,narcissus, freshly-cut hay, orange blossom, orchids, reseda, sweet pea,trefle, tuberose, vanilla, violet, wallflower, and the like.

As used herein olfactory effective amount is understood to mean theamount of compound in perfume compositions the individual component willcontribute to its particular olfactory characteristics, but theolfactory effect of the fragrance composition will be the sum of theeffects of each of the fragrance ingredients. Thus the compounds of theinvention can be used to alter the aroma characteristics of the perfumecomposition by modifying the olfactory reaction contributed by anotheringredient in the composition. The amount will vary depending on manyfactors including other ingredients, their relative amounts and theeffect that is desired.

The level of fragrance in the cationic polymer coated encapsulatedfragrance varies from about 5 to about 95 weight percent, preferablyfrom about 40 to about 95 and most preferably from about 50 to about 90weight percent on a dry basis. In addition to the fragrance other agentscan be used in conjunction with the fragrance and are understood to beincluded.

As noted above, the fragrance may also be combined with a variety ofsolvents which serve to increase the compatibility of the variousmaterials, increase the overall hydrophobicity of the blend, influencethe vapor pressure of the materials, or serve to structure the blend.Solvents performing these functions are well known in the art andinclude mineral oils, triglyceride oils, silicone oils, fats, waxes,fatty alcohols, diisodecyl adipate, and diethyl phthalate among others.

A common feature of many encapsulation processes is that they requirethe fragrance material to be encapsulated to be dispersed in aqueoussolutions of polymers, pre-condensates, surfactants, and the like priorto formation of the capsule walls. Therefore, materials having lowsolubility in water, such as highly hydrophobic materials are preferred,as they will tend to remain in the dispersed perfume phase and partitiononly slightly into the aqueous solution. Fragrance materials with Clog Pvalues greater than 1, preferably greater than 3, and most preferablygreater than 5 will thus result in micro-capsules that contain coresmost similar to the original composition, and will have less possibilityof reacting with materials that form the capsule shell.

One object of the present invention is to deposit capsules containingfragrance cores on desired substrates such as cloth, hair, and skinduring washing and rinsing processes. Further, it is desired that, oncedeposited, the capsules release the encapsulated fragrance either bydiffusion through the capsule wall, via small cracks or imperfections inthe capsule wall caused by drying, physical, or mechanical means, or bylarge-scale rupture of the capsule wall. In each of these cases, thevolatility of the encapsulated perfume materials is critical to both thespeed and duration of release, which in turn control consumerperception. Thus, fragrance chemicals which have higher volatility asevidenced by normal boiling points of less than 250° C., preferably lessthan about 225° C. are preferred in cases where quick release and impactof fragrance is desired. Conversely, fragrance chemicals that have lowervolatility (boiling points greater than 225° C.) are preferred when alonger duration of aroma is desired. Of course, fragrance chemicalshaving varying volatility may be combined in any proportions to achievethe desired speed and duration of perception.

In order to provide the highest fragrance impact from the fragranceencapsulated capsules deposited on the various substrates referencedabove, it is preferred that materials with a high odor-activity be used.Materials with high odor-activity can be detected by sensory receptorsat low concentrations in air, thus providing high fragrance perceptionfrom low levels of deposited capsules. This property must be balancedwith the volatility as described above. Some of the principles mentionedabove are disclosed in U.S. Pat. No. 5,112,688.

Further, it is clear that materials other than fragrances may beemployed in the system described here. Examples of other materials whichmay be usefully deposited from rinse-off products using the inventioninclude sunscreens, softening agents, insect repellents, and fabricconditioners, among others.

Encapsulation of fragrances is known in the art, see for example U.S.Pat. Nos. 2,800,457, 3,870,542, 3,516,941, 3,415,758, 3,041,288,5,112,688, 6,329,057, and 6,261,483. Another discussion of fragranceencapsulation is found in the Kirk-Othmer Encyclopedia.

Preferred encapsulating polymers include those formed frommelamine-formaldehyde or urea-formaldehyde condensates, as well assimilar types of aminoplasts. Additionally, capsules made via the simpleor complex coacervation of gelatin are also preferred for use with thecoating. Capsules having shell walls comprised of polyurethane,polyamide, polyolefin, polysaccaharide, protein, silicone, lipid,modified cellulose, gums, polyacrylate, polystyrene, and polyesters orcombinations of these materials are also functional.

A representative process used for aminoplast encapsulation is disclosedin U.S. Pat. No. 3,516,941 though it is recognized that many variationswith regard to materials and process steps are possible. Arepresentative process used for gelatin encapsulation is disclosed inU.S. Pat. No. 2,800,457 though it is recognized that many variationswith regard to materials and process steps are possible. Both of theseprocesses are discussed in the context of fragrance encapsulation foruse in consumer products in U.S. Pat. Nos. 4,145,184 and 5,112,688respectively.

Well known materials such as solvents, surfactants, emulsifiers, and thelike can be used in addition to the polymers described above toencapsulate the fragrance without departing from the scope of thepresent invention. It is understood that the term encapsulated is meantto mean that the fragrance material is substantially covered in itsentirety. Encapsulation can provide pore vacancies or interstitialopenings depending on the encapsulation techniques employed. Morepreferably the entire fragrance material portion of the presentinvention is encapsulated.

Particles comprised of fragrance and a variety of polymeric andnon-polymeric matrixing materials are also suitable for use. These maybe composed of polymers such as polyethylene, fats, waxes, or a varietyof other suitable materials. Essentially any capsule, particle, ordispersed droplet may be used that is reasonably stable in theapplication and release of fragrance at an appropriate time oncedeposited.

Particle and capsule diameter can vary from about 10 nanometers to about1000 microns, preferably from about 50 nanometers to about 100 micronsand most preferably from about 2 to about 15 microns. The capsuledistribution can be narrow, broad, or multi-modal. Each modal of themulti-modal distributions may be composed of different types of capsulechemistries.

Once the fragrance material is encapsulated a cationically chargedwater-soluble polymer is applied to the fragrance encapsulated polymer.This water-soluble polymer can also be an amphoteric polymer with aratio of cationic and anionic functionalities resulting in a net totalcharge of zero and positive, i.e., cationic. Those skilled in the artwould appreciate that the charge of these polymers can be adjusted bychanging the pH, depending on the product in which this technology is tobe used. Any suitable method for coating the cationically chargedmaterials onto the encapsulated fragrance materials can be used. Thenature of suitable cationically charged polymers for assisted capsuledelivery to interfaces depends on the compatibility with the capsulewall chemistry since there has to be some association to the capsulewall. This association can be through physical interactions, such ashydrogen bonding, ionic interactions, hydrophobic interactions, electrontransfer interactions or, alternatively, the polymer coating could bechemically (covalently) grafted to the capsule or particle surface.Chemical modification of the capsule or particle surface is another wayto optimize anchoring of the polymer coating to capsule or particlesurface. Furthermore, the capsule and the polymer need to want to go tothe desired interface and, therefore, need to be compatible with thechemistry (polarity, for instance) of that interface. Therefore,depending on which capsule chemistry and interface (e.g., cotton,polyester, hair, skin, wool) is used the cationic polymer can beselected from one or more polymers with an overall zero (amphoteric:mixture of cationic and anionic functional groups) or net positivecharge, based on the following polymer backbones: polysaccharides,polypeptides, polycarbonates, polyesters, polyolefinic (vinyl, acrylic,acrylamide, poly diene), polyester, polyether, polyurethane,polyoxazoline, polyamine, silicone, polyphosphazine, olyaromatic, polyheterocyclic, or polyionene, with molecular weight (MW) ranging fromabout 1,000 to about 1000,000,000, preferably from about 5,000 to about10,000,000. As used herein molecular weight is provided as weightaverage molecular weight. Optionally, these cationic polymers can beused in combination with nonionic and anionic polymers and surfactants,possibly through coacervate formation.

A more detailed list of cationic polymers that can be used to coat theencapsulated fragrance is provided below:

Polysaccharides include but are not limited to guar, alginates, starch,xanthan, chitosan, cellulose, dextrans, arabic gum, carrageenan,hyaluronates. These polysaccharides can be employed with:

-   -   (a) cationic modification and alkoxy-cationic modifications,        such as cationic hydroxyethyl, cationic hydroxy propyl. For        example, cationic reagents of choice are        3-chloro-2-hydroxypropyl trimethylammonium chloride or its epoxy        version. Another example is graft-copolymers of polyDADMAC on        cellulose like in Celquat L-200 (Polyquaternium-4),        Polyquaternium-10 and Polyquaternium-24, commercially available        from National Starch, Bridgewater, N.J.;    -   (b) aldehyde, carboxyl, succinate, acetate, alkyl, amide,        sulfonate, ethoxy, propoxy, butoxy, and combinations of these        functionalities. Any combination of Amylose and Mylopectin and        overall molecular weight of the polysaccharide; and    -   (c) any hydrophobic modification (compared to the polarity of        the polysaccharide backbone).

The above modifications described in (a), (b) and (c) can be in anyratio and the degree of functionalization up to complete substitution ofall functionalizable groups, and as long as the theoretical net chargeof the polymer is zero (mixture of cationic and anionic functionalgroups) or preferably positive. Furthermore, up to 5 different types offunctional groups may be attached to the polysaccharides. Also, polymergraft chains may be differently modified than the backbone. Thecounterions can be any halide ion or organic counter ion. U.S. Pat. No.6,297,203 and U.S. Pat. No. 6,200,554.

Another source of cationic polymers contain protonatable amine groups sothat the overall net charge is zero (amphoteric: mixture of cationic andanionic functional groups) or positive. The pH during use will determinethe overall net charge of the polymer. Examples are silk protein, zein,gelatin, keratin, collagen and any polypeptide, such as polylysine.

Further cationic polymers include poly vinyl polymers, with up to 5different types of monomers, having the monomer generic formula—C(R2)(R1)-CR2R3-. Any co-monomer from the types listed in thisspecification may also be used. The overall polymer will have a nettheoretical positive charge or equal to zero (mixture of cationic andanionic functional groups). Where R1 is any alkanes from C1–C25 or H;the number of double bonds ranges from 0–5. Furthermore, R1 can be analkoxylated fatty alcohol with any alkoxy carbon-length, number ofalkoxy groups and C1–C25 alkyl chain length. R1 can also be a liquidcrystalline moiety that can render the polymer thermotropic liquidcrystalline properties, or the alkanes selected can result in side-chainmelting. In the above formula R2 is H or CH3; and R3 is —Cl, —NH2 (i.e.,poly vinyl amine or its copolymers with N-vinyl formamide. These aresold under the name Lupamin 9095 by BASF Corporation), —NHR1, —NR1R2,—NR1R2 R6 (where R6=R1, R2, or —CH2-COOH or its salt), —NH—C(O)—H,—C(O)—NH2 (amide), —C(O)—N(R2)(R2′)(R2″), —OH, styrene sulfonate,pyridine, pyridine-N-oxide, quaternized pyridine, imidazolinium halide,imidazolium halide, imidazol, piperidine, pyrrolidone, alkyl-substitutedpyrrolidone, caprolactam or pyridine, phenyl-R4 or naphthalene-R5 whereR4 and R5 are R1, R2, R3, sulfonic acid or its alkali salt —COOH, —COO—alkali salt, ethoxy sulphate or any other organic counter ion. Anymixture or these R3 groups may be used. Further suitable cationicpolymers containing hydroxy alkyl vinyl amine units, as disclosed inU.S. Pat. No. 6,057,404.

Another class of materials are polyacrylates, with up to 5 differenttypes of monomers, having the monomer generic formula: —CH(R1)-C(R2)(CO—R3-R4)—. Any co-monomer from the types listed in this specificationmay also be used. The overall polymer will have a net theoreticalpositive charge or equal to zero (mixture of cationic and anionicfunctional groups). In the above formula R1 is any alkane from C1–C25 orH with number of double bonds from 0–5, aromatic moieties, polysiloxane,or mixtures thereof. Furthermore, R1 can be an alkoxylated fatty alcoholwith any alkoxy carbon-length, number of alkoxy groups and C1–C25 alkylchain length. R1 can also be a liquid crystalline moiety that can renderthe polymer thermotropic liquid crystalline properties, or the alkanesselected can result in side-chain melting. R2 is H or CH3; R3 is alkylalcohol C1–25 or an alkylene oxide with any number of double bonds, orR3 may be absent such that the C═O bond is (via the C-atom) directlyconnected to R4. R4 can be: —NH2, NHR1, —NR1R2, —NR1R2 R6 (where R6=R1,R2, or —CH2-COOH or its salt), —NH—C(O)—, sulfo betaine, betaine,polyethylene oxide, poly(ethyleneoxide/propylene oxide/butylene oxide)grafts with any end group, H, OH, styrene sulfonate, pyridine,quaternized pyridine, alkyl-substituted pyrrolidone or pyridine,pyridine-N-oxide, imidazolinium halide, imidazolium halide, imidazol,piperidine, —OR1, —OH, —COOH alkali salt, sulfonate, ethoxy sulphate,pyrrolidone, caprolactam, phenyl-R4 or naphthalene-R5 where R4 and R5are R1, R2, R3, sulfonic acid or its alkali salt or organic counter ion.Any mixture or these R3 groups may be used. Also, glyoxylated cationicpolyacrylamides can be used. Typical polymers of choice are thosecontaining the cationic monomer dimethylaminoethyl methacrylate (DMAEMA)or methacrylamidopropyl trimethyl ammonium chloride (MAPTAC). DMAEMA canbe found in Gafquat and Gaffix VC713 polymers from ISP. MAPTAC can befound in BASF's Luviquat PQ11 PN and ISP's Gafquat HS100.

Another group of polymers that can be used are those that containcationic groups in the main chain or backbone. Included in this groupare:

-   -   (1) polyalkylene imines such as polyethylene imine, commercially        available as Lupasol from BASF. Any molecular weight and any        degree of crosslinking of this polymer can be used in the        present invention;    -   (2) ionenes having the general formula set forth as        —[N(+)R1R2-A1-N(R5)-X—N(R6)-A2-N(+)R3R4-A3]n- 2Z-, as disclosed        in U.S. Pat. No. 4,395,541 and U.S. Pat. No. 4,597,962;    -   (3) adipic acid/dimethyl amino hydroxypropyl diethylene triamine        copolymers, such as Cartaretin F-4 and F-23, commercially        available from Sandoz;    -   (4) polymers of the general formula        —[N(CH3)2-(CH2)x-NH(CO)—NH—(CH2)y-N(CH3)2)—(CH2)z-O—(CH2)p]n-,        with x, y, z, p=1–12, and n according to the molecular weight        requirements. Examples are Polyquaternium 2 (Mirapol A-15),        Polyquaternium-17 (Mirapol AD-1), and Polyquaternium-18 (Mirapol        AZ-1).        Other polymers include cationic polysiloxanes and cationic        polysiloxanes with carbon-based grafts with a net theoretical        positive charge or equal to zero (mixture of cationic and        anionic functional groups). This includes cationic end-group        functionalized silicones (i.e. Polyquaternium-80). Silicones        with general structure: —[—Si(R1)(R2)-O—]x-[Si(R3)(R2)-O—]y-        where R1 is any alkane from C1–C25 or H with number of double        bonds from 0–5, aromatic moieties, polysiloxane grafts, or        mixtures thereof. R1 can also be a liquid crystalline moiety        that can render the polymer thermotropic liquid crystalline        properties, or the alkanes selected can result in side-chain        melting. R2 can be H or CH3 and        R3 can be —R1–R4, where R4 can be —NH2, —NHR1, —NR1R2, —NR1R2R6        (where R6=R1, R2, or —CH2-COOH or its salt), —NH—C(O)—, —COOH,        —COO— alkali salt, any C1–25 alcohol, —C(O)—NH2 (amide),        —C(O)—N(R2)(R2′)(R2″), sulfo betaine, betaine, polyethylene        oxide, poly(ethyleneoxide/propylene oxide/butylene oxide) grafts        with any end group, H, —OH, styrene sulfonate, pyridine,        quaternized pyridine, alkyl-substituted pyrrolidone or pyridine,        pyridine-N-oxide, imidazolinium halide, imidazolium halide,        imidazol, piperidine, pyrrolidone, caprolactam, —COOH, —COO—        alkali salt, sulfonate, ethoxy sulphate phenyl-R5 or        naphthalene-R6 where R5 and R6 are R1, R2, R3, sulfonic acid or        its alkali salt or organic counter ion. R3 can also be        —(CH2)x-O—CH2-CH(OH)—CH2-N(CH3)2-CH2—COOH and its salts. Any        mixture of these R3 groups can be selected. X and y can be        varied as long as the theoretical net charge of the polymer is        zero (amphoteric) or positive. In addition, polysiloxanes        containing up to 5 different types of monomeric units may be        used. Examples of suitable polysiloxanes are found in U.S. Pat.        Nos. 4,395,541 4,597,962 and U.S. Pat. No. 6,200,554. Another        group of polymers that can be used to improve capsule/particle        deposition are phospholipids that are modified with cationic        polysiloxanes. Examples of these polymers are found in U.S. Pat.        No. 5,849,313, WO Patent Application 9518096A1 and European        Patent EP0737183B1.

Furthermore, copolymers of silicones and polysaccharides and proteinscan be used (commercially available as CRODASONE brand products).

Another class of polymers include polyethyleneoxide-copropyleneoxide-co-butylene oxide polymers of any ethyleneoxide/propylene oxide/butylene oxide ratio with cationic groupsresulting in a net theoretical positive charge or equal to zero(amphoteric). The general structure is:

where R1, 2, 3, 4 is —NH2, —N(R)3- X+, R with R being H or any alkylgroup. R5,6 is —CH3 or H. Counter ions can be any halide ion or organiccounter ion. X, Y, may be any integer, any distribution with an averageand a standard deviation and all 12 can be different. Examples of suchpolymers are the commercially available TETRONIC brand polymers.

Suitable polyheterocyclic (the different molecules appearing in thebackbone) polymers include the piperazine-alkylene main chain copolymersdisclosed in Ind. Eng. Chem. Fundam., (1986), 25, pp.120–125, by IsamuKashiki and Akira Suzuki.

Also suitable for use in the present invention are copolymers containingmonomers with cationic charge in the primary polymer chain. Up to 5different types of monomers may be used. Any co-monomer from the typeslisted in this specification may also be used. Examples of such polymersare poly diallyl dimethyl ammonium halides (PolyDADMAC) copolymers ofDADMAC with vinyl pyrrolidone, acrylamides, imidazoles, imidazoliniumhalides, etc. These polymers are disclosed in Henkel EP0327927A2 and PCTPatent Application 01/62376A1. Also suitable are Polyquaternium-6(Merquat 100), Polyquaternium-7 (Merquats S, 550, and 2200),Polyquaternium-22 (Merquats 280 and 295) and Polyquaternium-39 (MerquatPlus 3330), available from Ondeo Nalco.

Polymers containing non-nitrogen cationic monomers of the general type—CH2-C(R1)(R2-R3-R4)- can be used with: R1 being a —H or C1–C20hydrocarbon. R2 is a disubstituted benzene ring or an ester, ether, oramide linkage. R3 is a C1–C20 hydrocarbon, preferably C1–C10, morepreferably C1–C4. R4 can be a trialkyl phosphonium, dialkyl sulfonium,or a benzopyrilium group, each with a halide counter ion. Alkyl groupsfor R4 are C1–C20 hydrocarbon, most preferably methyl and t-butyl. Thesemonomers can be copolymerized with up to 5 different types of monomers.Any co-monomer from the types listed in this specification may also beused.

Substantivity of these polymers may be further improved throughformulation with cationic, amphoteric and nonionic surfactants andemulsifiers, or by coacervate formation between surfactants and polymersor between different polymers. Combinations of polymeric systems(including those mentioned previously) may be used for this purpose aswell as those disclosed in EP1995/000400185.

Furthermore, polymerization of the monomers listed above into a block,graft or star (with various arms) polymers can often increase thesubstantivity toward various surfaces. The monomers in the variousblocks, graft and arms can be selected from the various polymer classeslisted in this specification and the sources below:

-   -   Encyclopedia of Polymers and Thickeners for Cosmetics, Robert        Lochhead and William From, in Cosmetics & Toiletries, Vol. 108,        May 1993, pp. 95–138;    -   Modified Starches: Properties & Uses, O. B. Wurzburg, CRC        Press, 1986. Specifically, Chapters 3, 8, and 10;    -   U.S. Pat. Nos. 6,190,678 and 6,200,554; and    -   PCT Patent Application WO 01/62376A1 assigned to Henkel.    -   Polymers, or mixtures of the following polymers:    -   (a) Polymers comprising reaction products between polyamines and        (chloromethyl) oxirane or (bromomethyl) oxirane. Polyamines        being 2(R1)N—[—R2-N(R1)-]_(n)—R2-N(R1)2, 2HN—R1NH2,        2HN—R2-N(R1)₂ and 1H-Imidazole. Also, the polyamine can be        melamine. R1 in the polyamine being H or methyl. R2 being        alkylene groups of C₁–C₂₀ or phenylene groups. Examples of such        polymers are known under the CAS numbers 67953-56-4 and        68797-57-9. The ratio of (chloromethyl) oxirane to polyamine in        the cationic polymer ranges from 0.05–0.95.    -   (b) Polymers comprising reaction products of alkanedioic acids,        polyamines and (chloromethyl) oxirane or (bromomethyl) oxirane.        Alkane groups in alkanedioic acids C0–C20. Polyamine structures        are as mentioned in (a). Additional reagents for the polymer are        dimethyl amine, aziridine and polyalkylene oxide (of any        molecular weight but, at least, di-hydroxy terminated; alkylene        group being C1–20, preferably C2–4). The polyalkylene oxide        polymers that can also be used are the Tetronics series.        Examples of polymers mentioned here are known under the CAS        numbers 68583-79-9 (additional reagent being dimethyl amine),        96387-48-3 (additional reagent being urea), and 167678-45-7        (additional reagents being polyethylene oxide and aziridine).        These reagents can be used in any ratio.

(c) Polyamido Amine and Polyaminoamide-epichlorohydrin resins, asdescribed by David Devore and Stephen Fisher in Tappi Journal, vol.76,No.8, pp. 121–128 (1993). Also referenced herein is“Polyamide-polyamine-epichlorohydrin resins” by W. W. Moyer and R. A.Stagg in Wet-Strength in Paper and Paperboard, Tappi Monograph SeriesNo. 29, Tappi Press (1965), Ch.3, 33–37.

The preferred cationically charged materials comprise reaction productsof polyamines and (chloromethyl) oxirane. In particular, reactionproducts of 1H-imidazole and (chloromethyl) oxirane, known under CASnumber 68797-57-9. Also preferred are polymers comprising reactionproducts of 1,6-hexanediamine,N-(6-aminohexyl) and (chloromethyl)oxirane, known under CAS number 67953-56-4. The preferred weight ratioof the imidazole polymer and the hexanediamine, amino hexyl polymer isfrom about 5:95 to about 95:5 weight percent and preferably from about25:75 to about 75:25.

The level of outer cationic polymer is from about 1% to about 3000%,preferably from about 5% to about 1000% and most preferably from about10% to about 500% of the fragrance containing compositions, based on aratio with the fragrance on a dry basis.

The weight ratio of the encapsulating polymer to fragrance is from about1:25 to about 1:1. Preferred products have had the weight ratio of theencapsulating polymer to fragrance varying from about 1:10 to about4:96.

For example, if a capsule blend has 20 weight % fragrance and 20 weight% polymer, the polymer ratio would be (20/20) multiplied by 100(%)=100%.

The present invention, the encapsulated fragrance is well suited forwash-off products. Wash-off products are understood to be those productsthat are applied for a given period of time and then are removed. Theseproducts are common in areas such as laundry products, and includedetergents, fabric conditioners, and the like; as well as personal careproducts which include shampoos, hair rinses, body washes, soaps and thelike.

As described herein, the present invention is well suited for use in avariety of well-known consumer products such as laundry detergent andfabric softeners, liquid dish detergents, automatic dish detergents, aswell as hair shampoos and conditioners. These products employ surfactantand emulsifying systems that are well known. For example, fabricsoftener systems are described in U.S. Pat. Nos. 6,335,315, 5,674,832,5,759,990, 5,877,145, 5,574,179, 5,562,849, 5,545,350, 5,545,340,5,411,671, 5,403,499, 5,288,417, 4,767,547 and 4,424,134. Liquid dishdetergents are described in U.S. Pat. Nos. 6,069,122 and 5,990,065;automatic dish detergent products are described in U.S. Pat. Nos.6,020,294, 6,017,871, 5,968,881, 5,962,386, 5,939,373, 5,914,307,5,902,781, 5,705,464, 5,703,034, 5,703,030, 5,679,630, 5,597,936,5,581,005, 5,559,261, 4,515,705, 5,169,552, and 4,714,562. Liquidlaundry detergents which can use the present invention include thosesystems described in U.S. Pat. Nos. 5,929,022, 5,916,862, 5,731,278,5,565,145, 5,470,507, 5,466,802, 5,460,752, 5,458,810, 5,458,809,5,288,431, 5,194,639, 4,968,451, 4,597,898, 4,561,998, 4,550,862,4,537,707, 4,537,706, 4,515,705, 4,446,042, and 4,318,818. Shampoo andconditioners that can employ the present invention include U.S. Pat.Nos. 6,162,423, 5,968,286, 5,935561, 5,932,203, 5,837,661, 5,776,443,5,756,436, 5,661,118, 5,618,523, 5,275,755, 5,085,857, 4,673,568,4,387,090, 4,705,681.

We have discovered that the present invention is advantageously appliedto products, including fabric rinse conditioners, having a pH of lessthan 7, preferably less than about 5 and most preferably less than about4.

A better product, including wash-off products such as fabric rinseconditioner is also obtained when the salt level is limited. Theimprovement in the fabric rinse conditioner is noted by a longer lastingand/or improved delivery of fragrance. One method of improving thedelivery of the encapsulated fragrance is to limit the amount of salt inthe product base. Preferably the level of salt in the rinse conditionerproduct is less than or equal to about 1 weight percent by weigh in theproduct, preferably less than about 0.5 weight percent and mostpreferably less than about 0.1 weight percent.

More specifically we have discovered that limiting the level of calciumchloride will improve the delivery of the fragrance using theencapsulated fragrance of the present invention. Improved fragrancedelivery is provided by limiting the amount of calcium chloride to lessthan about 2 weight percent, typically less than 1 weight percent andmore preferably less than 0.5 weight percent. As it is known in the art,calcium chloride is added to control viscosity of the formulations, sothere is trade-off between the viscosity and fragrance delivery. We havediscovered that limiting the level of calcium chloride level as setforth above is particularly advantageous in fabric rinse conditionerproducts.

Another means for improving the performance of delivery of theencapsulated fragrance of the present invention is to limit the level ofsome softening agents. We have discovered that limiting the softeningactives, such as triethanolamine quaternary, diethanolamine quaternary,ACCOSOFT cationic surfactants (Stepan Chemical), or ditallow dimethylammonium chloride (DTDMAC), to an amount of from about 5 to about 40weight percent of the product, preferably from about 5 to about 30 andmore preferably from about 5 to 15 weight percent of a fabric rinseconditioner product will improve the performance of the fragrance. Theabove softening agents are well known in the art and are disclosed inU.S. Pat. Nos. 6,521,589 and 6,180,594.

Yet another means for improving fragrance delivery of the presentinvention is to limit the level of the non-ionic surfactants employed inthe product, including a fabric softening product. Many non-ionicsurfactants are known in the art and include alkyl ethoxylate,commercially available as NEODOL (Shell Oil Company), nonyl phenolethoxylate, TWEEN surfactants (ICI Americas Inc.), and the like. We havediscovered that the encapsulated fragrance of the present invention areadvantageously used when the non-ionic surfactant level is below about 5weight percent of the product, preferably less than about 1 weightpercent and most preferably less than 0.5 weight percent.

Yet another means for enhancing the fabric softener product is to limitthe level of co-solvent included in the fabric softener in addition towater. Reducing the level of co solvents such as ethanol and isopropanolto less than about 5 weight percent of the product, preferably less thanabout 2 and most preferably less than about 1 weight percent of thefabric softener product has been found to improve fragrance delivery.

Improved fragrance performance includes longer lasting fragrance,improved substantivity of the fragrance on cloth or the ability toprovide improved fragrance notes, such as specific fragrance notesthrough the use of the present invention.

While the above description is primarily to fabric rinse conditionerproducts, additional studies for shampoos, detergent and other cleaningproducts have also led to preferred embodiments for these products aswell.

As was found for fabric rinse conditioners, additional studies havedetermined that lower pH is desirable for the delivery of fragrance whenused in the product base. The preferred bases are neutral or mildlyacidic, preferably having a pH of 7, more preferably less than about 5and most preferably less than about 4 for shampoos, detergent and othercleaning products.

We have found that powder detergent and other cleaning products provideenhanced fragrance delivery when the material coating the encapsulatingpolymer is also neutral or slightly acidic. Preferred materials areNaHSO4, acetic acid, citric acid and other similar acidic materials andtheir mixtures. These materials have a pH of less than about 7,preferably less than about 5 and most preferably less than about 4.

As was described with fabric rinse conditioners, lower surfactant levelswere advantageously employed in shampoos, detergents and other cleaningproducts bases with the present invention. The level of surfactant ispreferably less than about 0.30, more preferably less than about 20 andmost preferably less than about 10 weight percent of the product base. Asimilar finding was found with preferred levels of salt in shampoos,detergents and other cleaning products as was found in fabric rinseconditioners. The salt level is preferably less than about 5 weightpercent, more preferably less than about 2 and most preferably less than0.5 weight percent of the product.

Lower solvent levels found in the base improves the fragrance deliveryin shampoos, detergents and other cleaning products as well. Solvents,include but are not limited to, ethanol, isopropanol, dipropylene glycolin addition to the water base and the hydrotope level is preferably lessthan 5 weight percent, preferably less than about 2 and most preferablyless than. 1 weight percent of the total product base.

A preferred surfactant base for shampoos, detergents and other cleaningproducts was found to be ethoxylated surfactants such as alkylethoxylated sulfates, (C₁₂–C₁₄) (ethylene oxide)nSO₄M; or ethoxylatedcarboxylate surfactants (C₁₂–C₁₄)(Ethylene oxide)nCOOM where n is from 1to about 50 and M is Na⁺, K⁺ or NH4⁺ cation. Other preferred anionicsurfactants are alkoyl isethionates, such as sodium cocoly isethionate,taurides, alpha olefin sulphonates (i.e., Bioterge, Stepan Corporation),sulfosuccinates, such as Standapol SH-100 (Cognis) and disodium laurethsulfosuccinate (Stepan Mild SL3-BA, Stepan Corporation). A morepreferred class of surfactants for use in the present invention waszwitterionic surfactants such as the alkyl amine oxides, amidealkylhydroxysultaines like amidopropyl hydroxyl sultaine (Amphosol CS-50,Stepan Corporation), amphoacetates, such as sodium cocamphoacetate(Amphosol IC, Stepan Corporation), betaines and sulfobetaines.Zwitterionic surfactants are disclosed in greater detail in U.S. Pat.No. 6,569,826. Other commercially available surfactants are AMPHOSOLseries of betaines (Stepan Chemical); TEGOTIAN by Goldschmidt; andHOSTAPAN and ARKOPAN by Clariant

The most preferred surfactant system to be employed with theencapsulated fragrance system of the present invention was found to benon-ionic surfactants. Nonionic surfactants that may be used include theprimary and secondary alcohol ethoxylates, especially the C₈–C₂₀aliphatic alcohols ethoxylated with an average of from 1 to 50 moles ofethylene oxide per mole of alcohol, and more especially the C₁₀–C₁₅primary and secondary aliphatic alcohols ethoxylated with an average offrom 1 to 10 moles of ethylene oxide per mole of alcohol. Otherethoxylated nonionic surfactants that are suitable are polyethyleneglycol (MW=200–6000) esters of fatty acids, ethylene oxide-propyleneoxide-butylene oxide block copolymers such as the Pluronic and Tetronicpolymers made by BASF, and ethoxylated alkanolamides such as PEG-6cocamide (Ninol C-5, Stepan Corporation). Non-ethoxylated nonionicsurfactants include alkylpolyglycosides, glycerol monoethers,polyhydroxyamides (glucamide), polyglycerol fatty acid esters, alkylpyrrolidone-based surfactants (Surfadone LP-100 and LP300, ISPCorporation), dialkyl phthalic acid amides (distearyl phthalic acidamide or Stepan SAB-2 by Stepan Corporation), alkyl alkanolamides, suchas Laureth Diethanolamide (Ninol 30-LL, Stepan Corporation). Thesenonionic surfactants are disclosed in U.S. Pat. No. 6,517,588.

In addition, Gemini surfactants can be used, such as the Geminipolyhydroxy fatty acid amides disclosed in U.S. Pat. No. 5,534,197.Furthermore, structured liquids can be used that contain lamellarvesicles or lamellar droplets, as disclosed in WO 9712022 A1 and WO9712027 A1, U.S. Pat. Nos. 5,160,655, and 5,776,883.

Polymers that are known as deposition aids, and in a preferredembodiment are also cationic can be found in the following resources:

The rinse-off products that are advantageously used with the polymerencapsulated fragrance of the present invention include laundrydetergents, fabric softeners, bleaches, brighteners, personal careproducts such as shampoos, rinses, creams, body washes and the like.These may be liquids, solids, pastes, or gels, of any physical form.Also included in the use of the encapsulated fragrance are applicationswhere a second active ingredient is included to provide additionalbenefits for an application. The additional beneficial ingredientsinclude fabric softening ingredients, skin moisturizers, sunscreen,insect repellent and other ingredients as may be helpful in a givenapplication. Also included are the beneficial agents alone, that iswithout the fragrance.

While the preferred coating materials may be simply dissolved in waterand mixed with a suspension of capsules prior to addition to the finalproduct, other modes of coating use and application are also possible.These modes include drying the coating solution in combination with thecapsule suspension for use in dry products such as detergents, or usinghigher concentrations of coating such that a gel structure is formed, orcombining the coating material with other polymers or adjuvants whichserve to improve physical characteristics or base compatibility. Dryingor reducing the water content of the capsule suspension prior to coatingaddition is also possible, and may be preferable when using some coatingmaterials. Further, when using some coating materials it is possible toadd the coating to the application base separately from the encapsulatedfragrance.

Solvents or co-solvents other than water may also be employed with thecoating materials. Solvents that can be employed here are (i) polyols,such as ethylene glycol, propylene glycol, glycerol, and the like, (ii)highly polar organic solvents such as pyrrolidine, acetamide, ethylenediamine, piperazine, and the like, (iii) humectants/plasticizers forpolar polymers such as monosaccharides (glucose, sucrose, etc.), aminoacids, ureas and hydroxyethyl modified ureas, and the like, (iv)plasticizers for less polar polymers, such as diisodecyl adipate (DIDA),phthalate esters, and the like.

Rheology modifiers should be selected carefully to insure compatibilitywith the deposition agents. Preferred are nonionic, cationic andamphoteric thickeners, such as modified polysaccharides (starch, guar,celluloses), polyethylene imine (Lupasol WF, BASF Corporation),acrylates (Structure Plus, National Starch and Chemical Company) andcationic silicones.

The coating polymer(s) may also be added to a suspension of capsulesthat contain reactive components such that the coating becomeschemically (covalently) grafted to the capsule wall, or the coatingpolymer(s) may be added during the crosslinking stage of the capsulewall such that covalent partial grafting of the coating takes place.

Further, if stability of the capsule and coating system is compromisedby inclusion in the product base, product forms which separate the bulkof the base from the fragrance composition may be employed. The cationiccoated polymer particles of the present invention may be provided insolid and liquid forms depending on the other materials to be used. Inorder to provide the cationic coated polymer in a dry form, it ispreferable that the materials be dried using drying techniques wellknown in the art. In a preferred embodiment the materials are spraydried at the appropriate conditions. The spray dried particles may alsobe sized to provide for consistent particle size and particle sizedistribution. One application in which it would be advantageous toinclude dry particles of the present invention would be incorporated ina powdered laundry detergent. Alternatively wet capsule-coating slurriesmay be absorbed onto suitable dry powders to yield a flowable solidsuitable for dry product use.

The present invention also includes the incorporation of a silicone or asiloxane material into a product that contains encapsulated fragrancesof the present invention. As used herein silicone is meant to includeboth silicone and siloxane materials. Also included in the definition ofsilicone materials are the cationic and quaternized of the silicones.These materials are well known in the art and include both linear andbranched polymers.

In addition to silicones, the present invention also includes the use ofmineral oils, triglyceride oils, polyglycerol fatty acid esters, andsucrose polyester materials in a similar matter as the siliconematerials. For brevity, these materials are understood to be included inthe term silicone as used in this specification unless noted to thecontrary. Those with skill in the art will also appreciate that it ispossible to incorporate a silicone in combination with mineral oils andthe like in carrying out the present invention.

The silicone material is preferably admixed to the encapsulatedfragrance-containing product after the fragrance materials areencapsulated. Optionally, the silicone material may be mixed directlywith the product base either before or after the encapsulated fragrancehas been added.

Suitable silicone materials include amodiemthicone, polymethylalkylsiloxanes, polydimethylalkyl siloxanes, dimethicone, dimethiconecopolyol, dimethiconol, disiloxane, cyclohexasiloxane, cyclomethicone,cyclopentasiloxane, phenyl dimethicone, phenyl trimethicone, siliconequaternarary materials including silicone quaternium-8, and siliconequaternium-12, trimethylsiloxyamidodimethicone, trimethylsiloxysilicateand the like. These materials are commercially well known materials andare available from suppliers such as Dow Corning, Shin-Etsu, WackerSilicones Corporation and the like. The preferred silicon is Dow Corning245 Fluid (Dow Corning, Midland Mich.), which is described as containinggreater than about 60 weight percent decamethylcyclopentasiloxane andless than or equal to about 4 weight percent dimethylcyclosiloxanes.

Amino functional silicone oils such as those described in U.S. Pat. Nos.6,355,234 and 6,436,383 may also be used in the present invention.

Preferably the silicone materials of the present invention have amolecular weight (Mw) of from about 100 to about 200,000, preferablyfrom about 200 to about 100,00 and most preferably from about 300 toabout 50,000.

The viscosity of the silicone materials is typically from 0.5 to about25, preferably from about 1 to about 15 and most preferably from about 2to about 10 millimeters²sec−1 using the Corporate Test Method asdescribed in the Dow Corning product brochures.

The level of silicone used in the present invention varies by product,but is typically less than 10 percent by weight, typically from about0.5 to about 8 weight percent of the total weight of product. Preferablythe silicon level is from about 2 to about 6 and most preferably fromabout 3 to about 5 weight percent of the total weight of the product.

The silicone fluid can be added to a wide array of products in order toenhance the delivery of fragrance. Suitable products include fabricconditioners and detergents, personal care products such as shampoos,liquid soap, body washes and the like; as well as in applications suchas fine fragrances and colognes.

For example, a representative formulation for a fabric softener rinseproduct would include the following materials:

cationic quaternary ammonium softeners from about 3 to about 30 weightpercent;

the encapsulated fragrance product of the present invention from about0.1 to about 5 weight percent; and

a silicone oil form about 1 to about 10 weight percent.

The remainder of the fabric softener product may additionally contain,without limitation, brighteners, dispersibility aids, surfactants,stabilizers, soil release agents and water.

Without wishing to be bound by any theory it is believed that thesilicone fluid prevents the encapsulated fragrance material fromleaching from the capsule. Although the encapsulation materials areprovided to prevent the loss of fragrance before usage, it is believedthat the surfactants found in detergents, fabric conditioners, shampoosand other wash-off products over time leach some of the fragrance fromthe capsule during storage and before use. The addition of the siliconefluids to the fragrance-containing capsule materials is believed to coatthe encapsulation materials with a layer of silicone that prevents theleaching of the fragrance. Another rationale for the improvement of thedelivery of fragrance by the addition of silicone oils is that the oilsfill vesicles in the product base. The product base such as a detergent,contains high levels of surfactant, and it is theorized that the highlevel of surfactant in the product bases over time removes the fragrancefrom the capsule. The addition of silicone to the slurry containing theencapsulated fragrance is theorized to slow the leaching of thefragrance by the surfactant, thereby providing additional and longerlasting fragrance to be delivered over time.

In another embodiment of the present invention, we have discovered thatthe cationic coating is not required and that the inclusion of siliconin the encapsulated mixture can provide satisfactory performance in thedelivery of the fragrance. In this embodiment of the invention, thefragrance is encapsulated by the polymeric materials described above,and the level of silicon described above is provided to the encapsulatedfragrance.

More specifically the present invention is directed to a compositioncomprising a fragrance material, said fragrance material encapsulated bya polymer to provide a polymer encapsulated fragrance, said polymerencapsulated fragrance further provided with a silicone material. Thisembodiment differs from other embodiments of the present invention inthat the cationic polymer is not provided. The silicone oil is providedwithout a cationic polymer present. A description of the suitablesilicone oils is provided above as well as the level of the silicon oilthat is used.

The mixture mentioned above can be provided into a wide range ofproducts, including rinse-off products including but not limited tofabric rinse conditioners, detergents, shampoos, body washes, and othercleaning products.

A preferred embodiment of the present invention is exemplified by thefollowing formulation:

cationic quaternary ammonia softeners from about 3 to about 30 weightpercent;

polymer encapsulated capsules containing fragrance from about 0.1 toabout 5 weight percent; and

silicone oils from about 1 to about 10 weight percent.

The remainder of the formulation comprises water, bleaching agents,stain removers, and other ingredients known to those with skill in theart.

The mechanism of action of the present invention is not completelyunderstood at this time. It is thought that the cationic polymersolution coats and associates with the polymeric capsules, thusimparting a positive charge which interacts with either the base orsubstrate in such a way as to substantially improve capsule depositionto the substrate surface.

It should be noted that the cationic character of the polymer coatingused is not sufficient to determine whether it is functional with regardto improving capsule or particle deposition. Without wishing to be boundby theory, it is hypothesized that while cationic charge provides anaffinity to the normally anionic substrates of interest (i.e. hair,skin, and cloth), other physical characteristics of the polymer are alsoimportant to functionality. Additionally, interactions between thecapsule or particle surface, base ingredients, and the coating polymerare thought to be important to improving deposition to a givensubstrate.

Use of the coating systems described below allows for more efficientdeposition of capsules, particles, and dispersed droplets that arecoated by the cationically charged polymer. Without wishing to be boundby any theory it is believed that the advantages of the presentinvention is created by the combination of the cationically chargedcoating which is helpful in adhering to the substrate to which theproduct is applied with a capsule or particle containing fragrance. Oncethe encapsulated particle is adhered to the substrate we have found thatthe encapsulated fragrance can be delivered by the fracturing orcompromising of the polymer coating by actions such as brushing hair,movement of the fabric, brushing of the skin etc.

One measurement of the enhancement of the present invention indelivering the fragrance and other ingredients of the present inventionis done by headspace analysis. Headspace analysis can provide a measureof the fragrance material contained on the desired substrate provided bythe present invention. The present invention will provide a much higherlevel of fragrance on the substrate compared to the amount of fragrancedeposited on the substrate by conventional means. As demonstrated by thefollowing examples, the present invention can deliver more than abouttwice the level of fragrance to a substrate than common approaches,preferably more than about three times the level of fragrance andpreferably more than about five times the level of fragrance thantraditional approaches.

For example, this may be determined by measuring the level of fragranceimparted to a test hair swatch containing fragrance in a shampoo byconventional means as compared to the level of fragrance imparted by thepresent invention. The same fragrance should be used and similar testhair pieces should be washed in a similar manner. After brushing torelease the fragrance from the hair, the level of fragrance on the testhair swatches of the control and the fragrance of the present inventioncould be measured by headspace analysis. Due to the superior adhesion offragrance to hair by the present invention, the headspace analysis ofthe respective samples will demonstrate an improved level of fragranceas compared to fragrance applied by conventional means.

To better control and measure the fragrance release upon brushing orrubbing from a substrate (i.e., hair or cotton cloth), a fixed-weight ofthe washed and dried substrate will be placed in a custom-made glassvessel containing SILCOSTEEL (Resteck Corp., Bellefont, Pa.) treatedsteel ball bearings. Headspace will be collected from the vessel using aTenax trap (Supelco, Inc., Bellafonte, Pa.) upon equilibration. A secondheadspace will be collected after the substrate-containing vessel isshaken along with the steel beads on a flat bed shaker for 20 minutes.Fragrance present in the headspace from unshaken and shaken substratesand subsequently absorbed in the Tenax traps is desorbed through aGerstel thermal desorption system (Gersteel, Inc., Baltimore, Md.).Desorbed fragrance volatiles are injected into a gas chromatograph(Hewlett-Packard., Model Agilent 6890) equipped with a flame ionizationdetector. Area counts of individual fragrance components, identifiedbased on the retention time, are then collected and analyzed.

All U.S. patents and patent applications cited herein are incorporatedby reference as if set forth herein in their entirety.

These and additional modifications and improvements of the presentinvention may also be apparent to those with ordinary skill in the art.The particular combinations of elements described and illustrated hereinare intended only to represent only a certain embodiment of the presentinvention and are not intended to serve as limitations of alternativearticles within the spirit and scope of the invention. All materials arereported in weight percent unless noted otherwise. As used herein allpercentages are understood to be weight percent.

EXAMPLE 1 Preparation of Fragrance

The following ingredients were mixed to formulate the fragrance that wasused in the following examples. Unless noted to the contrary allingredients are available from International Flavors & Fragrances Inc.,New York, N.Y., known to those with skill in the art as IFF.

Ingredients Parts by weight Ethyl-2-methyl 7.143 valerate Limonene 7.143Dihyro myrcenol 7.143 Phenyl ethyl 7.143 alcohol Benzyl acetate 7.143Dimeth benzyl 7.143 carbonate acetate Methyl nonyl 7.143 acetaldehydeCYCLACET (IFF) 7.143 LILIAL (Givaudan) 7.143 Hexyl salicylate 7.143Tonalid 7.143 Geraniol 7.143 Methoxy naphthalene 7.143 Beta ionone 7.143

EXAMPLE 2 Preparation of Bare (Uncharged) Capsules and CationicPolymer-Coated Capsules

Melamine-formaldehyde capsule slurry (made by Celessence InternationalLtd., West Molesey, Surrey, UK) that contains approximately 32% byweight of the fragrance and 57% by weight of water was used as bare(uncharged) capsules in the following examples. To make themelamine-formaldehyde capsule slurry, a copolymer of poly acrylamide andacrylic acid was first dispersed in water together with a methylatedmelamine-formaldehyde resin. Fragrance was then added into the solutionwith high speed shearing to form small droplets. Curing of the polymericfilm over the fragrance droplets as capsule wall affected by increasingthe solution pH to polymerize the polymers followed by heating thesolution to 50 to 85° C.

Cationic polymer-coated capsules were prepared by incorporating amixture of cationic polymers during the curing stage of the barecapsule-making process specified above. The finished cationic capsuleslurry contains 25.6% by weight of the fragrance and 56.9% by weight ofwater.

EXAMPLE 3 Preparation of Control Fragrance- and Bare Capsules-ContainingShampoo for Hair Swatch Washing

The control shampoo was prepared by mixing the neat fragrance at 0.75%by weight in 30 grams of model shampoo base for 5 minutes. Shampoo thatcontained bare capsules without a cationic coating was prepared the sameway by mixing the melamine-formaldehyde capsule slurry in shampoo toobtain 0.75% by weight fragrance. The resulting fragrance orcapsules-containing shampoo was added into 570 grams of 40° C. warmwater and mixed for 2 minutes. Four virgin hair swatches (approximately2.5 grams each) were added into the warm wash liquor and shaken foranother 2 minutes in a 40° C. water bath. Swatches were taken out fromthe wash liquor and rinsed sequentially in three glass jars that eachcontained 600 grams of clean warm water. Washing and rinsing wererepeated once and excess water from hair was removed. Hair swatches wereline-dried for 24 hours followed by sensory evaluation and analyticalheadspace analysis.

EXAMPLE 4 Preparation of Cationic Capsules-Containing Shampoo for HairSwatch Washing

Cationic polymer-coated capsules prepared according to Example 2 wereused to mix in 30 grams of model shampoo base to obtain a fragrancelevel of 0.75% by weight. The resulting shampoo was used to wash fourvirgin hair swatches according to the procedures described in Example 3.Hair swatches were line-dried for 24 hours followed by sensoryevaluation and analytical headspace analysis.

EXAMPLE 5 Sensory Evaluation and Headspace Analysis of Hair Swatches

Dry hair swatches were evaluated by a panel of four people using theintensity scale of 0 to 5, where 0=none, 1=weak, 2=moderate, 3=strong,4=very strong, and 5=extremely strong. Sensory scores were recordedbefore and after hair swatches were rubbed by hand. Deposition andrelease of fragrance and capsules were assessed using the purge-and-trapmethod followed by gas chromatography analyses on 5.0 grams of dry hairswatches before and after shaking with steel beads in enclosed vessels.Averaged sensory scores and total headspace area counts of the variablestested were reported in the following:

Sensory score Sensory score Hair swatch variable (before rubbing) (afterrubbing) Neat fragrance 1.7 2.0 Encapsulated fragrance 2.0 2.0 withoutcationic polymer Encapsulated fragrance 3.0 3.7 coated with cationicpolymers

Encapsulated Encapsulated fragrance fragrance with without cationiccationic Neat fragrance polymer polymers Un- Un- Un- CHEMICAL shakenShaken shaken Shaken shaken Shaken Ethyl-2-methyl 278 681 117 676 2,6447,274 valerate Limonene 2,081 4,157 765 2,527 11,014 37,382 Dihydro 5 614 99 408 3,009 myrcenol Phenyl ethyl 18 67 27 225 52 168 alcohol Benzylacetate 16 71 13 55 75 212 Geraniol 0 0 0 0 7 59 Dimethyl 9 181 5 88 7514,441 benzyl carbonate acetate Methyl nonyl 25 313 5 76 495 2,976acetaldehyde CYCLACET 10 139 74 66 383 2,301 (IFF) Methoxy 21 76 9 72174 405 naphthalene Beta ionone 0 24 0 12 109 1,074 LILIAL 0 25 68 11775 691 (Givaudan) Hexyl 0 9 3 5 15 92 salicylate Tonalid 0 0 0 0 0 12Fragrance 2,463 5,804 1,090 4,018 16,202 60,096 total area count

In this example, sensory results suggest that unchargedmelamine-formaldehyde bare capsules do not to deposition hair throughshampoo washing. In addition, it is believed that friction created fromrubbing was the primary key to release fragrance of deposited capsuleson hair washed with cationic capsules-containing shampoo. Rubbed hairswatches washed with shampoo with cationic capsules showed appreciablesensory intensity improvement over those washed with shampoo containingeither neat fragrance or uncharged bare capsules. These observationswere supported by the headspace analyses, where the headspace areacounts of hair washed with cationic capsules were 10 and 15-fold overthose of hair washed with neat fragrance and bare capsules after thehair was rubbed by steel beads. A significant increase of headspace areacounts of hair washed with cationic capsules before rubbing alsodemonstrated the benefit of the cationic polymers in enhancing capsuledeposition.

EXAMPLE 6 Preparation of Control Fragrance- and Capsules-ContainingPowder Detergent for Fabric Swatch Washing

The control powder detergent was prepared by mixing the neat fragranceprepared in Example 1 above, at 0.3% by weight in 2.13 grams ofcommercially purchased powder detergent (unfragranced TIDE, Procter &Gamble). Powder detergent that contained bare capsules was prepared thesame way by mixing melamine-formaldehyde capsule slurry in detergent toobtain 0.3% by weight fragrance. The resulting fragrance- orcapsules-containing detergent was added into 1-liter water in aseparation glass funnel. Three terry cotton swatches (approximately 2grams each) were added into the wash liquor and shaken for 15 minutesbefore the wash liquor was drained from the bottom of each funnel.Excess water was removed from swatches by syringe and swatches wererinsed with 1-liter water for additional 5 minutes using the sameapparatus. Rinsing was repeated once before swatches were line-dried for24 hours followed by sensory evaluation and analytical headspaceanalysis.

EXAMPLE 7 Preparation of Cationic Capsules-Containing Powder Detergentfor Fabric Swatch Washing

Fragrance-containing capsules with a cationic coating were prepared asdescribed in Example 2 were used to mix in 2.13 grams of commerciallypurchased detergent TIDE (P&G) to obtain a fragrance level of 0.3% byweight. The resulting detergent was used to wash three fabric swatchesaccording to the procedures described in Example 6. Fabric swatches wereline-dried for 24 hours followed by sensory evaluation and analyticalheadspace analysis.

EXAMPLE 8 Sensory Evaluation and Headspace Analysis of Fabric SwatchesWashed with Powder Detergent

Dry fabric swatches were evaluated by a panel of four people using theintensity scale of 0 to 5, where 0=none, 1=weak, 2=moderate, 3=strong,4=very strong, and 5=extremely strong. Sensory scores were recordedbefore and after hair swatches were rubbed by hand. Deposition andrelease of fragrance and capsules were assessed using the purge-and-trapmethod followed by GC analyses on two dry fabric swatches before andafter shaking with steel beads in enclosed vessels. Averaged sensoryscores and total headspace area counts of the three variables testedwere reported in the following:

Sensory score Sensory score Fabric swatch variable (before rubbing)(after rubbing) Neat fragrance 1.0 0 Encapsulated fragrance 0 0.8without cationic polymer Encapsulated fragrance 1.5 2.5 coated withcationic polymers

Encapsulated Encapsulated fragrance coated fragrance without withcationic Neat fragrance cationic polymer polymers Un- Un- Un- CHEMICALshaken Shaken shaken Shaken shaken Shaken Ethyl-2-methyl 0 0 0 15 31 93valerate Limonene 86 98 82 189 654 4,392 Dihydro 5 10 3 14 9 12 myrcenolPhenyl ethyl 740 1,258 503 845 327 761 alcohol Benzyl acetate 689 1,991207 669 167 578 Geraniol 0 0 6 39 0 0 Dimethyl 4 6 3 4 14 196 benzylcarbonate acetate Methyl nonyl 16 77 3 8 20 162 acetaldehyde CYCLACET 711 7 11 8 11 (IFF) Methoxy 0 0 0 0 0 9 naphthalene Beta ionone 0 0 2 0 027 LILLIAL 0 10 4 8 0 19 (Givaudan) Hexyl 0 11 3 7 0 10 salicylateTonalid 0 0 0 0 0 0 Fragrance total 1,547 3,472 823 1,809 1,230 6,270area count

Sensory results demonstrate that uncharged bare capsules slightlyimproved fragrance perception on rubbed cotton swatches over the neatfragrance, non-encapsulated, when used with the powder detergent. Thisslight intensity increase, however, was not supported by the gaschromatography headspace area counts, probably due to the low overalllevel of components. On the contrary, capsules coated with cationicpolymers of the present invention improved sensory intensity appreciablyon the swatches upon rubbing. This was confirmed analytically that 3.5and 1.8 fold increase of headspace area counts of rubbed swatches washedwith cationic capsules over those washed with bare capsules and neatfragrance.

EXAMPLE 9 Preparation and Sensory Results of Capsules-Containing PowderDetergent for Machine Washing

The control powder detergent was prepared by mixing the neat fragrance,selected as having a pleasing floral note, at 0.35% by weight in anunfragranced detergent base similar to commercially available products.Powder detergent that contained bare capsules was prepared by absorbingmelamine-formaldehyde capsule slurry with Aerosil 200 (DegussaGoldschmidt Aktengesellschaft Inc.) at a 75/25 weight ratio followed bymixing it in the powder detergent to obtain 0.35% by weight fragrance.Cationic capsules-containing powder detergent was prepared in the samemanner by mixing the free flow powder of Aerosil 200/cationic capsuleslurry in the detergent to obtain the 0.35% by weight fragrance. Thesefragrance/capsules-containing bases were also stored at 37° C./70%relative humidity condition for stability testing.

A standard set that weighted 2200 grams of towels, T-shirt, pillowcases,and tea towels was used for the Miele (Model W362) wash machine washing.A standard program of 40° C., short program, and 900 rpm spin rate wasutilized. Approximately 100 milliliters of each detergent sample wasused for washing experiment. Sensory ratings were obtained on dry clothsby a trained panel, panelists rubbed the towels for 1 to 2 seconds priorto smelling them, after cloths were dried in open air for a day. Initialand 2 weeks storage sensory ratings were record as follows.

Sensory score Sensory score Fabric towel variable (fresh samples)(Stored samples) Neat fragrance 1.2 1.6 Encapsulated fragrance 1.4 1.5without cationic polymer Encapsulated fragrance 3.4 2.6 coated withcationic polymers

Sensory results confirmed the benefit of cationic polymers of thepresent invention used with capsules when incorporated in the powderdetergent for large-scale machine wash. Although the sensory intensitydecreased after the detergent was stored at an accelerated condition for2 weeks, the performance of cationic capsules-containing detergent wasstill perceived as being far better than that of neat fragrance and barecapsules without the cationic coating.

EXAMPLE 10 Preparation of Control Fragrance- and BareCapsules-Containing Fabric Softener for Fabric Swatch Washing

A control was prepared by mixing the neat fragrance at 1.0% by weight in1.0 gram of liquid fabric softener. Three different fabric softenerbases were used, which were commercial Downy Ultra fragrance-free fabricsoftener (Procter & Gamble), model fabric softeners #1 containing 9weight % softening surfactants, and model fabric softener #2 containing5 weight percent softening surfactant. Fabric softener that containedcapsules without cationic coating was prepared the same way by mixingthe melamine-formaldehyde capsule slurry in fabric softener to obtain1.0% by weight fragrance. The resulting fragrance- orcapsules-containing softener was added into 1-liter water in aseparation glass funnel. Three fabric cotton swatches (approximately 2grams each) were added into the wash liquor and stirred for 10 minutesbefore the wash liquor was drained from the bottom of each funnel.Excess water was removed from swatches by syringe and swatches wereline-dried for 24 hours followed by sensory evaluation and analyticalheadspace analysis.

EXAMPLE 11 Preparation of Cationic Capsules-Containing Fabric Softenerfor Fabric Swatch Washing

Fragrance-containing capsules coated with cationic polymers wereprepared as described in Example 2 and were mixed in 1.0 gram of liquidfabric softener to obtain a fragrance level of 1.0% by weight. Theresulting fabric softener was used to wash three fabric swatchesaccording to the procedures described in Example 9. Fabric swatches wereline-dried for 24 hours followed by sensory evaluation and analyticalheadspace analysis.

EXAMPLE 12 Sensory Evaluation and Headspace Analysis of Fabric SwatchesWashed with Liquid Softener

Dry fabric swatches were evaluated by a panel of four people using theintensity scale of 0 to 5, where 0=none, 1=weak, 2=moderate, 3=strong,4=very strong, and 5=extremely strong. Sensory scores were recordedbefore and after fabric swatches were rubbed by hand. Deposition andrelease of fragrance and capsules were assessed using the purge-and-trapmethod followed by GC analyses on two dry fabric swatches before andafter stirring with steel beads in enclosed vessels. Averaged sensoryscores and headspace area counts of the three variables tested werereported in the following:

Sensory Sensory score score Fabric (before (after Fabric swatch variableConditioner Base rubbing) rubbing) Neat fragrance P&G DOWNY 1.3 1.5ULTRA Encapsulated fragrance P&G DOWNY 1.2 2.0 without cationic ULTRApolymer Encapsulated fragrance P&G DOWNY 1.0 2.2 coated with cationicULTRA polymers Neat fragrance Simulated model 0.9 1.0 fabric softenerproduct base 1 Encapsulated fragrance Simulated model 2.3 3.5 withoutcationic fabric softener polymer product base 1 Encapsulated fragranceSimulated model 2.5 4.5 coated with cationic fabric softener polymersproduct base 1 Neat fragrance Simulated model 1.8 2.3 fabric softenerproduct base 2 Encapsulated fragrance Simulated model 1.8 3.0 withoutcationic fabric softener polymer product base 2 Encapsulated fragranceSimulated model 2.3 4.5 coated with cationic fabric softener polymersproduct base 2

Commercial P&G DOWNY Fabric Softener Encapsulated Encapsulated Fragrancefragrance coated without cationic with cationic Neat fragrance polymerpolymers Un- Un- Un- CHEMICAL shaken Shaken shaken Shaken shaken ShakenEthyl-2-methyl 14 21 195 2,038 157 3,957 valerate Limonene 32 63 8,45681,512 4,291 82,294 Dihydro 18 122 43 683 20 759 myrcenol Phenyl ethyl 00 0 117 0 0 alcohol Benzyl acetate 71 311 147 775 127 606 Geraniol 0 0 010 0 11 Dimethyl 0 2 137 4,146 24 2,733 benzyl carbonate acetate Methylnonyl 3 50 77 1,975 26 1,415 acetaldehyde CYCLACET 0 12 56 1,932 191,289 (IFF) Methoxy 0 25 5 68 0 101 naphthalene Beta ionone 0 4 5 600 0457 LILIAL 0 26 3 261 0 209 (Givaudan) Hexyl 0 39 0 148 0 81 salicylateTonalid 0 8 0 19 0 11 Fragrance total 138 683 9,124 94,284 4,664 93,923area count

Encapsulated Encapsulated Fragrance fragrance coated without cationicwith cationic Neat fragrance polymer polymers Un- Un- Un- CHEMICALshaken Shaken shaken Shaken shaken Shaken Simulated model fabricsoftener product base 1 Ethyl-2-methyl 0 0 552 8,325 1,077 19,188valerate Limonene 59 84 6,792 92,094 9,331 161,851 Dihydro 41 178 11 87881 2,533 myrcenol Phenyl ethyl 0 0 0 0 0 227 alcohol Benzyl acetate 29731 38 503 486 1,983 Geraniol 0 0 0 5 0 17 Dimethyl 5 18 34 3,271 1445,102 benzyl carbonate acetate Methyl nonyl 20 115 28 2,027 90 2,740acetaldehyde CYCLACET 0 16 12 1,580 72 2,719 (IFF) Methoxy 0 13 4 139 15180 naphthalene Beta ionone 10 51 0 359 7 793 LILIAL 0 28 0 208 6 353(Givaudan) Hexyl 0 42 0 65 0 170 salicylate Tonalid 0 10 0 10 0 18Fragrance total 164 1,286 7,471 109,464 11,309 197,874 area countSimulated model fabric softener product base 2 Ethyl-2-methyl 0 0 8788,607 796 15,925 valerate Limonene 45 75 10,421 123,405 8,389 174,473Dihydro 15 41 118 1,684 37 1,978 myrcenol Phenyl ethyl 0 0 0 218 0 95alcohol Benzyl acetate 573 5,309 3,147 7,987 1,103 6,662 Geraniol 0 0 022 0 16 Dimethyl 0 9 217 4,854 55 4,467 benzyl carbonate acetate Methylnonyl 6 124 173 2,951 41 3,015 acetaldehyde CYCLACET 0 12 122 2,599 262,886 (IFF) Methoxy 0 8 13 119 7 173 naphthalene Beta ionone 0 4 16 8860 842 LILIAL 0 34 10 456 0 468 (Givaudan) Hexyl 0 44 0 191 0 218salicylate Tonalid 0 13 0 24 0 29 Fragrance total 639 5,673 15,115154,003 10,454 211,247 area count

Sensory results demonstrate that cationic polymers did enhance capsuledeposition, thereby providing stronger sensory perception on rubbedcotton swatches, especially rinsed with simulated model fabric softenerproducts 1 and 2 as opposed to commercially purchased DOWNY fabricsoftener without the cationic coated capsules. Sensory results aresupported by the analytical headspace area counts in most cases.

EXAMPLE 13 Preparation and Sensory Results of Capsules-Containing RinseConditioners for Machine Washing

The following example employed a pleasant smelling floral fragranceadded to a concentrated model fabric softener base employing aquaternary fabric softening base at a level of 1.0%, this was used asthe control. Two additional samples were prepared. One sample by addingbare capsules containing the same fragrance and another by addingcationic capsules containing the same fragrance, both to give theequivalent of 1.0% fragrance.

A standard set that weighted 2200 grams of towels, T-shirt, pillowcases,and tea towels was used for the Miele (Model W362) wash machine washing.A standard program of 40° C., short program, and 900 rpm spin rate wasutilized. Approximately 100 milliliters of a regular commercial powdereddetergent was used for washing the samples and 35 ml of each of theabove mentioned concentrated fabric conditioner samples were added tothe conditioner drawer of the washing machines.

After line drying in the open air for 1 day sensory data was recorded.Trained panelists rubbed the cloths for 1 to 2 seconds prior to smellingthem.

The cloths were then kept in an open environment for a further 14 days,they were assessed again at 7 and 14 days.

1 day 7 days 14 days Samples in conc. TEA Quat Fab con dry dry dryFloral control Neat oil 1.84 1.66 0.64 Floral encapsulated fragrance3.66 3.91 3.15 with cationic polymer coating Floral encapsulatedfragrance 2.63 2.62 1.84 (bare)

In the above table the cationic polymer coating greatly enhances thefragrance perception from dry fabric up to and possibly beyond 14 daysafter washing, easily outperforming the neat oil and capsules withoutthe coating.

EXAMPLE 14

The following products were purchased at a local store for testing:

-   1. DOWNY ULTRA, Fabric Softener (Procter & Gamble), Free of dyes and    perfumes;-   2. SUAVITEL Field Flower, Fabric Softener (Colgate Palmolive    Company); and-   3. SNUGGLE Ultra, Pure & Gentle, (Unilever)-dye free product.

Since the above products contained varying levels of surfactant,fragrance was added proportionally to the surfactant, and the level ofsurfactant in the rinse water was adjusted so that the fragrance levelwas consistent in all the products.

A bench-top rinse procedure, followed by ambient air drying, was used toevaluate deposition on cotton cloth swatches. Analysis was conducted byevaluating the headspace by gas chromatography over the dried cloth,both without stirring and after stirring with steel balls to break thedeposited capsules and release the fragrance. Cationically coated(COATED CAPSULES) similar to Example 2 described above and theencapsulated fragrance was compared against the non-encapsulated or neatfragrance.

Results are presented below:

Unstirred Stirred System (Nanogram/Liter) (Nanogram/Liter) DOWNY ULTRA +NEAT 17 85 Fragrance DOWNY ULTRA + COATED 690 8674 CAPSULES SUAVITEL +NEAT 62 270 Fragrance SUAVITEL + COATED 798 10725 CAPSULES SNUGGLE +NEAT 51 124 Fragrance SNUGGLE + COATED 682 7727 CAPSULES

As can be seen from the above results, fragrance deposition as measuredby using headspace analysis was slightly better using the SUAVITEL base.This could be due to the use of different softening agents and/orsurfactants or other additives present in the base. When the capsuleproducts were stored at elevated temperature (37° C.), performancedeclined for all the samples, although differences in stability wereobserved. The SUAVITEL product was most stable, the SNUGGLE product lessso, and the DOWNY ULTRA product was found to be the most unstable whenusing the encapsulated fragrance of the present invention. Withoutwishing to be bound by any specific theory, the differences in theperformance of the fragrance is most likely due to fragrance leachingfrom the capsules. The amount of fragrance leaching from the capsules isbelieved to be dependent on the specific surfactants used, the level ofsurfactants, pH and other factors in the product bases.

1. A composition comprising: a fragrance material; said fragrancematerial encapsulated by a polymer to provide a polymer encapsulatedfragrance; the polymer encapsulated fragrance is further coated by apolyamine product, said polyamine product is a reaction product of1H-Imidazole and an oxirane material.
 2. The composition of claim 1wherein the polyamine product is a reaction product of melamine and anoxirane material.
 3. The composition of claim 1 wherein the polyamineproduct is a reaction product of alkanedioic acids, polyaniines and anoxirane.
 4. The composition of claim 1 wherein the polyamine product isa polyamino amine or polyaminoamide-oxirane reaction product.
 5. Thecomposition of one of claims 1, 2, 3, or 4 wherein the oxirane materialis selected from the group consisting of (chloromethyl) oxirane,(bromomethyl) oxirane and mixtures thereof.
 6. The composition of claim1 wherein the fragrance is a liquid thereby providing a liquid core tothe polymer encapsulated fragrance.
 7. The fragrance of claim 1, whereinthe fragrance material is not water soluble.
 8. The composition of claim1 wherein the fragrance material is from about 10 to about 50 weightpercent of the composition.
 9. The composition of claim 1 which isincorporated into a product selected from the group consisting of apersonal care, fabric care and cleaning products.
 10. The composition ofclaim 9 wherein the personal care product is selected from the groupconsisting of hair shampoos, hair rinses, bar soaps, and body washes.11. A composition comprising: a fragrance material; said fragrancematerial encapsulated by a polymer to provide a polymer encapsulatedfragrance; the polymer encapsulated fragrance is further coated by apolyamine product, said polyamine product is a reaction product ofpolyamines and (chloromethyl) oxirane or (bromomethyl) oxirane and anadditional cationic polymers.
 12. A wash-off product comprising thecomposition of claim 1 and a silicone material and having a calciumchloride level of from about 0.05 to about 1 weight percent.
 13. Thewash-off product of claim 12 wherein the wash-off product is a fabricrinse conditioner.
 14. The wash-off product of claim 12 having asurfactant level of from about 5 to about 30 weight percent.
 15. Thewash-off product of claim 12 wherein the silicone level is from about0.5 to 8 weight percent of product.
 16. The wash-off product of claim 15wherein the wash-off product is a fabric rinse conditioner.
 17. Thewash-off product of claim 16 further comprising a softening agent at alevel of from about 10 to about 20 weight percent.